Cation-active polychloride containing an esterified polyaminoether, and method of making same



Patented Aug. 28, 1951 UNITED STATES PATENT OFFICE CATION-ACTIVE POLYCHLORIDE CON TAIN ING AN ESTERIFIED POLYAMINOETHER, AND METHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Dcl., a corporation of Delaware No Drawing. Original application March 11, 1948, Serial No. 14,397. Divided and this application February 18, 1949, Serial No. 77,293

8 Claims. 1

Our invention relates to new chemical products or compounds and to the manufacture of same, our present application being a division of our co-pending application Serial No. 14,397, filed March 11, 1948, Patent No. 2,472,573, issued June 7, 1949.

One object of our invention is to provide a new chemical compound or product that is particularly adapted for use as a demulsifier for crude oil emulsions, but which is also capable of various other uses. 7

Another object of our invention is to provide a practicable method for manufacturing said new chemical product or compound.

The material, compound, product, or composition of matter herein described is a cation-active polychloride. Such cation-active polychlorides are obtained by reaction between an esterified monoamino alcohol or an esterified monoamino alcohol ether, as subsequently described, and diglycol chloroformate sometimes referred to as diethylene glycol bis (chloroformate), the formula for such compound being as follows:

It is well known that triethanolamine can be esterified with higher fatty acids having 8 to 22 carbon atoms, for example, such as lauric acid, stearic acid, oleic acid, and the like, so as to yield a compound of the formula:

The product of esterified tertiary ethenolamines such as the esters of triethanolamine, ethyldiethanolamine, diethylethanolamine, etc., have been described in the literature, and particularly the patent literature. The best known examples are those of the following formula:

in which RC0 is the acyl radical of the higher fatty acid having 8 to 22 carton atoms, and R1 and R2 are selected from the class of alkyl radicals having not more than 4 carbon atoms (methyl, ethyl, propyl, or butyl) ethanol radicals, or ethanol radicals which have been treated with a mole of ethylene oxide or a mole of glycide.

If one reacts triethanolamine with 3, 2, and 1 mole of ethylene oxide, the following compounds are obtained:

Similarly, if triethanolamine is treated with glycide, or if it is converted into the alcoholate and then treated with glycerolchlorhydrin, one then obtains compounds such as the following:

ethanolamine, is to use the glyceride as a matter of economy. The alcoholysis reaction which takes place may be indicated in the following manner:

OH. czHr-N R. O O O OH. 02114 R. O O O-GaHa OH. GzH N R. C O O OH. C2H4 OH. C2H4-N 0H. CzHi 3 OH.CaH|N C3H5(OH)B OH.C2H4

The temperature employed for such reaction is generally 175 or somewhat less, in order to avid etherization of the amino alcohol. Even so, the glycerol liberated from the glyceride may combine with the triethanolamine before acylation takes place. In any event, the final product may be in part an acylated monoamino ether alcohol. Such compound is identical with the one obtained by e'sterifying or acylating triethanolamine after first treating such an amine with glycide or the equivalent reaction previously described.

Recapitulating what has been said, it is to be noted that the acyl radical may be attached to the nitrogen atom through the radical which contains the ether linkage. Thus, in the'broadest aspect, the acylated monoami'noalcohols and the acylated monoamino alcohol ethers herein contemplated as a reactant for combination with diglycol chloroformate, may be indicated by the following formula:

/R1 RCQQRSN in which RCOis 'the acyl 'radical of a high' molal monocarboxy acid, particularly a higher fatty acid, and especially, one having 8 to 22 carbon atoms. R1 and R2 are selected from the monova lent radicals H QzHn, Cs 1, C4 9, 'CElIlO H CtHcO daHlOH Q OH 021140 CaHO CaHs and R3 is selected from the divalent radicals C2 4 05x40 elm The expression higher molecular weight carboxy acids is anexpression frequently employed to refer to certain ergamc acids, particularly monocarboxy acids, having'more than 6 carbon atoms and generally less than carbon atoms. The commonest examples include the detergentforming acids,'i. e., those acids which combine with alkalies toproduce soap or -soap-like bodies. The detergent forming acids, in turn, include naturally-occurring fatty acids,'resin acids, such as abietic acid,naturally-occurring petroleum acids such as naphthenic acids, and carboxy acids produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which havesome'what similar characteristics and are derived from somewhat different sources, and are different in structure, but can be included in the broad generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic alicyclic, fatty, aromatic, 'h'ydroaromatic, and aralkyl acids including caprylic acid, butyric acid, heptylic acid, 'caproic acid, capric acid, pimelic acid, sebacic acid, erucic acid, saturated and unsaturated higher molecular weight aliphatic acids, such as the higher fatty acids containing at least 8 carbon atoms, and including in addition to those mentioned, melissic acid, stearic acid, oleic acid, ricinoleic acid, diricinoleic acid, triricinoleic acid, polyricinoleic acid,

ricinostearolic acid, ricinoleyl lactic acid, acetyl- ,4 ricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, undecylenic acid, palmitic acid, mixtures of any two or more of the above-mentioned acids or other acids, mixed higher fatty acids derived from animal or ve etable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils, such as those men- ;tioned; hydroxy and alphahydroxy higher carboxylic, aliphatic and fatty acids, such as hy- :I droxystearic acid, dihydroxypalmitic acid, dihydroxysteario acid, dihydroxybehenic acid, alphahydroxy capric acid, alphahydroxy stearic acid, alphahydroxy palmitic acid, alphahydroxy lauric acid, alphahydroxy myristic acid, alphahydroxy cocoanut oil mixed fatty acids, alphahydroxy margaric acid,-alphahydroxy 'arachidic acid, and the like; fatty and similar acids derived from various-waxeasuch-as beeswax, spermaceti, montan wax, Japan wax, coccerin, and carnauba wax. -Suchacids-include carnaubic acid, cerotic hydrogenated ca'rboxydiphenyl, "'naphthenic, and

abietic acid; aralkyl and-aromatic acids, such as hexahydrobenzoic 'acid, hydrogenated naphtlioic, hydrogenated poly -carboxy*- diphenyl, naphthenic, andabietic-acid; aralkyl and ammatic acids, such as benzoic --'acid. Twitchell fatty acids, naphthoic acid, 'carboxy-diphenyl, pyridine carboxylic acid, hydroxybenzoic acid, and the like.

Other suitable-acids include phenylstearic acid, benzoylnonylic acid, camph'olic acid, fencholic acid, cetyloxybutyric acid, cetyloxyacetic acid, etc.

Another source of suitable acids are those commonly referred to as lac acids, such, for example, as the acids'derived-from shellac. Such acids include various vpolyhydroxy acids, for example, aleuritic acid, shelloic acid, andkerrolic acid.

As is well known, one may use substituted acids in which someother non-functional constituent enters the structure of the'fatty acid. For instance, one may use aryl-,' hydroxy-, alkoxy-, keto and aminoderivatives. Generally speaking, however, it is always-preferable to use the unsubstituted acid, particularly free from substituents which contain either oxygen'or nitrogen atoms. Generally speaking, the introduction of hydrocarbon radicals, regardless of source, has little effect except in altering the-hydrophile-hydrophobe balance.

One may also employ the blown" or oxidized acids, such as blOtVIll'iOi-ll'OliC acid, blown oleic, or estolides derived from blown oils, such as blown castor oil, blown soyabean oil, etc.

As previously stated, the acylated monoamino alcohols or the acylated monoamino alcohol ethers herein employed as reactants, are well known compounds and have been described frequently in the literature, particularly-the patent literature. Our preference is to obtain them from higher fatty acids or higher fatty acid glycerides, and we particularly prefer to employ ricinoleic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, or the glycerides which are a source of such fatty acids such as castor oil, neats-footoil, lard oil, soyabean oil, stearine, etc;

We have also found naphthenic acids, particularly those bearing a molecular weight from slightly above 200 to slightly less than 400, to be particularly desirable as reactants. We have also employed resin acids such as rosin, abietic acid, etc. Such compounds are obtainable in the manner described are are sometimes obtained conveniently by treating an acylated monoamino alcohol or acylated monoamino alcohol ether with one or two moles of ethylene oxide or glycide.

Such reactants,*all of which are well known, may be exemplified by the following formulae, in which RC is the acyl radical of a higher fatty acid of the kind described, or the acyl radical of the naphthenic acids, as described, or the acyl radical of a resin acid such as abietic acid, etc'.:

CzH4OH R C O O C2H4N Y canoe Alkyl R C O O CQHlN CzH OH (Alkyl: methyl, ethyl, propyl, or butyl) I Alkyl R C O O C2H4N Alkyl (Alkyl:methyl, ethyl, propyl, or bntyl) 021140 C2H4OH RC 0 O C2H4 (32H. 0 02H; OH

R o o o 02H:

C2H4 0 C2H4 OH G2H| 0 02B OH RC 0 0 02340 O|H4N 02H 0 Gail. OH

021140 C8HA(OH)2 R C 0 O CBHAN C2H4O CsH(OH)g 021140 lHl( )2 R o o o ciH N Alkyl (Aikyl: methyl, ethyl, propyl, or butyl) 021 40 C3H5(OH)2 RCOOCaHuOCzHgN E 021340 Ca a(0 )2 C2H40 OS K M R O O 0 0 13 0 OzH4N H Alkyl (Alkyl methyl, ethyl, propyl, or butyl) CATION-ACTIVE POLYCHLORIDE Example 1 Two gram moles of the monoricinoleyl ester of triethanolamine (858 grams) is mixed with one gram mole of diglycol chloroformate (58 grams). The mixture was placed in a flask with a suitable stirrin device and reflux condenser and heated at 160 to 180 C. for one hour. The mixture showed a tendency to foam when first warmed, but as soon as the reaction started, the

foaming tendency decreased. The particular triethanolamine ester employed gave a cloudy solution in water. Diglycol chloroformate is, of course, water-insoluble. The resultant product was sufliciently soluble in water at the end of the reaction period to give a perfectly clear solution and showed a presence of chloride ions.

CATION-ACTIVE POLYCHLDRIDE Example 2 The same procedure was followed as in Example 1, preceding, except that two gram moles of the oleic acid ester (826 grams) was employed instead of two gram moles of the ricinoleic acid ester, In all other respects the procedure was identical with that described in Example 1.

CATION-ACTIVE POLYCHLORIDE Example 3 The same procedure was followed as in Example Lpreceding, except that, two gram moles of the stearic acid ester (830 grams) was em-- ployed instead of two gram moles of the ricinoleic acid ester. In all other respects the procedure: was identical with that described in Example 1..

' CATION-ACTIVE POLYCHLORIDE Example 4 The same procedure was followed as in Ex'-- ample 1, preceding, except that two gram moles of the abietic acid ester (866 grams) was employed instead of two gram moles of the ricinoleic acid ester. In all other respects the procedure was identical with that described in Example 1.

CATION-ACTIVE POLYCHLORIDE Example 5 CATION ACTIVE POLYCHLORIDE Example 6 Thesame procedure was followed as in the five preceding examples, except that, instead of using the triethanolamine ester, there was employed the ester of monoethyldiethanolamine. For convenience, the weights employed are indicated by reference to the subsequent table. The table shows the molecular weights of the ester.

' As in Example 1, the amount employed was two gram moles in each instance.

CA'IION-ACTIVE POLYCHLORIDE Example 7 The same procedure was followed as in the six preceding examples, except that, instead of using the triethanolamine, ester, there was employed the ester of For convenience, the weights employed are indicated by reference to the subsequent table. The table shows the molecular weights of the ester. As in Example'l, the amount employed was two gram moles in each instance.

CATION-ACTIVEPOLYCHLORIDE Molecularwig'ht mono-actyl derivative Example 8 a m a The same procedure was followed as in the Q "seven preceding examples, except that, instead of g using the triethanolamine ester. there was emg N g m 5 ployed the ester of g E; g? 5 E g ;ogn..ooinion i g g q 5 5 5 N g g H 5 E \c e a g g a g 2 a a a a For convenience, the weights employed are ing ,3 2 f g g dicated by reference to the subsequent table. g z Z 2 mi The table shows the molecular weights 0% the 503 ester. As in Example 1, the amount emp oye'd Blcinoleic ,429 413 am 457 651 was two gram moles in each instance. $2533 I: :12 iii; 22? C-ATION-ACTIVE POLYCI-ILORLIDE tittiarmaa 565 E p 3st 340 488 384 578 43 The same procedure was followed as in the eight preceding examples'except that, instead of it IS Obvwus a m se n Instances. h y using the triethanolamine ester, there was emdroxyl available for reaction with the die y ployed the ester of chloroformate, may be furnished by the acyl V V n. radical of the mono-carboxy acid, as in the case NllciHmcsfifloHhh of ricinoleic acid, hydroxystearic acid, dihydroxy- For convenience, the weights employed are instearic acid, and other hydroxylated acids obdicated by reference to the subsequent table. Gained by t aOlJ O of yd o peroxide on un- The table shows the molecular weights f the saturated fatty acids including undecylenic acid. ester. As in Example 1, the amount employed In light of What has been said immediately prewas twogram moles i e h instanc ceding, it is obvious that the amine employed i M c may also include types such as diethylethanola- -CATIONqACLIVEPOLYCHLORLDE mine, dipropylethanolamine, dibutylethanola- Example 10 mine, and the comparable dialkyl derivatives of ,7 i c l glyceramine. Similarly, an amine of the last same: procedm'e was followed as m the mentioned type may be treated with one mole of nine precedmgexamples, except that, ir1st of ethylene oxide prior to acylation, or, inversely,

using the triethanolamme ester there was the dialkyl ethanola-mines may be treated with a ployed the ester of mole of glycide or an equivalent reaction em- 7 oinionn ployed prior to acylation.

40 When prepared from the simplest and most readily available reactants, i. e., 18 carbon fatty cmocsflfmmi acids and triethanolamine, the structures ob- For convenience, e Wei ht p y d' tained are indicated by the following reaction d a d by reference u qu a l and formula, assuming that, if the acyl radical 'The table shows the molecular weights of the has an alcoholic h ydroxyl, reaction takes place eS S n Example he u fi p y 45 preferentially at the ethanol hydroxyl, for the was two gram moles in each instance. reason that the latter is a primary alcoholic rad- This type of acylated ester can be obtained by ical and thef'o'rr'ner is a secondary alcoholic radia number of procedures, two of which are as cal.

RoodozH 2 NCzH OHCKOCOCxHtQCzHtOCO) c1 Ho..c'2Hi V RC G 9. 9534; CEHl-O 0 CR uoamoooi'oclniocimoooooinm +-2Ho1 Ebro/2H1 CsH.QN

acooom CzHLOOCR of] I: Noiniooo.ooln.oosn,oooooinig :1

H0.0!H| V canon of follows: Materials of thekind herein specified are use- (1) Treat triethanolamine with one mole of ful as Wetting detergent, and leveling agents in glycide and then acylate. the laundry, textile and dyeing industries; as

(2) Prepare the acylatedester of tri'ethanolwetting agents and detergents in the acid washamine and thentreat withone mole'of'glycide; If ing of fruit, in the acid washing of building this procedure is followed, the acyl radical is atstone and briclg; as a wetting agent and spreader tached to the ethoxy radical. If the first procein the application of asphalt in roadbuilding and dine is followed, one: may obtain a mixture of the like; .asa constituent ofsoldering flux prepaacylated derivatives in which part are charac- 7O rations; as a flotation reagent in the flotation terized by attachment of theacyl radical to the separation of various minerals; for flocculation ethoxy radical and part by attachment of the and coagulation of various aqueous suspensions acyl radical to the ether radical. containing negatively charged particles, such as 3 For convenience, the-following table is subseWage.,coalIwashing Waste water, and various stitutetl: I 75 tradewastes, and'the like; as germicides, insecr 9 10 ticides, emulsifiers for cosmetics, spray oils, 5. The product of claim 8, wherein RC is a water-repellent textile finish, etc. These uses are ricinoleyl radical. by no means exhaustive. The most important 6. The product of claim 3, wherein RC0 is an phase of the present invention, as far as industrial oleyl radical.

application goes, is concerned with the use of 7. The product of claim 3, wherein RC0 is a the materials previously described as demulsifiers linoleyl radical. for water-in-oil emulsions, and more specifically, 8. A method for obtaining a cation-active polyemulsions of water or brine in crude petroleum. chloride, characterized by reacting diglycol chlo- Having thus described our invention, what we roformate with a hydrcxylated mono-acylatecl claim and desire to secure by Letters Patent is: amine of the following formula:

1. A cation-active polychloride which is the R reaction product of diglycol chloroformate and 1 a hydroxylated monoacylated amine of the follow- RCOORN ing formula:

R, in which RC0 is the acyl radical of a higher fatty ROOOREN/ acid having at least 8 and not more than 22 carbon atoms and R1 and R2 are selected from the monovalent radicals in which RC0 is the acyl radical of a higher fatty CH3, CHB, 0am, CHo, acid having at least 8 and not more than 22 car- H OH bon atoms and R1 and R2 are selected from the 0 z 40 (Jz toE monovalent radicals CH3, C2Ht, CsH1, C4H0 /OH CzH4OH 26 (hHAO 031140 03H! CgHAO 02H OH OH and R3 is selected from the divalent radicals OIHAOCiHAO 03H; 0 H

I 4 0H e H 00 H and R3 is selected from the divalent radicals 3o 2 02H 0x 100211 C3H40 01H; H zm with the further proviso that there be at least H one occurrence of an alcoholic hydroxyl radical in the radicals R, R1, R2, and R3. with the further proviso that there be at least MELVIN DE GROOTE one occurrence of an alcoholic hydroxyl radical BE ARD KEISER in the radicals R, R1, R2, and R3. RNH

2. The product of claim 1, wherein the ratio REFERENCE ITED of the hydroxylated mono-acylated amine to 40 s C The following references are of record in the chloroformate 1S 2 to 1. i

3. A product of the following formula: me of th 5 patent- RCOO.C|H4 H C2HLOOOR [G1] I: NCaHeOOC.OO:H4OO:H4OOOOO1H4N 110.0, CzH4.0N 01} wherein RC0 is the acyl radical of a higher fatty UNITED STATES PATENTS acid having at least 8 and not more than 22 'car- Number Name Date 1011 amms- 2,468,180 De Groote et a1. A r. 26, 1949 4. The product of claim 3, wherein RC0 is the 2,463,181 De Groote et aL B 26, 1949 acyl radical of an unsaturated fatty acid having 7 57 De G m et aL June 7 1949 18 carbon atoms, 

1. A CATION-ACTIVE POLYCHLORIDE WHICH IS THE REACTION PRODUCT OF DIGLYCOL CHLOROFORMATE AND A HYDROXYLATED MONOACYLATED AMINE OF THE FOLLOWING FORMULA: 